CN112023721A - Visible light driven self-cleaning carbon nitride multifunctional composite film and preparation method and application thereof - Google Patents
Visible light driven self-cleaning carbon nitride multifunctional composite film and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 120
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 154
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 111
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 111
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- 235000015523 tannic acid Nutrition 0.000 claims abstract description 66
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
The invention provides a preparation method of a visible light driven self-cleaning carbon nitride multifunctional composite film, which comprises the following steps: s1, realizing g-C pair by complexation of tannic acid and ferric salt3N4The modified product is subjected to vacuum filtration to realize surface modification of the PVDF membrane, and g-C is prepared3N4a/TA composite membrane; s2, g-C obtained in step S13N4The g-C is prepared by loading ferric hydroxide on the/TA composite membrane3N4a/TA @ FeOOH-x composite membrane; the visible light driven self-cleaning carbon nitride multifunctional composite film prepared by the invention has the beneficial effects that: (1) the water-based paint has good hydrophilic performance and underwater super-oleophobic wettability, and has higher pure water flux; (2) the surfactant-stabilized oil-water emulsion has a good separation effect, the separation effect on the emulsion is over 99.0 percent, and the surfactant-stabilized oil-water emulsion has excellent anti-pollution performance; (3) has good visible light catalytic degradation performance.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a visible light driven self-cleaning carbon nitride multifunctional composite film, and a preparation method and application thereof.
Background
The membrane separation technology has the characteristics of low cost, simple operation and the like, is generally considered to have huge application prospect in the aspect of treating oily sewage, can realize sewage reclamation through the technology, lightens the environmental problem, and further relieves the current situation of water resource shortage. However, in the process of oil-water separation, the surface of the membrane material is very easy to be adsorbed by pollutants to cause serious membrane pollution, block membrane pores, reduce the separation efficiency of the membrane and shorten the service life of the oil-water separation membrane. At present, the traditional oil-water separation membrane generally has the problem of membrane pollution, and the practical application of the membrane separation technology in the field is severely limited. Improving the anti-pollution performance of the membrane material is an important research direction of the current membrane separation technology, and has great significance for the practical application of the membrane separation technology in water treatment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a visible light driven self-cleaning carbon nitride multifunctional composite film, a preparation method and application thereof by regulating and controlling the surface components and the microstructure of the film.
The invention provides a preparation method of a visible light driven self-cleaning carbon nitride multifunctional composite film, which comprises the following steps:
s1, realizing g-C pair by complexation of tannic acid and ferric salt3N4The modified product is subjected to vacuum filtration to realize surface modification of the PVDF membrane, and g-C is prepared3N4a/TA composite membrane;
s2, g-C obtained in step S13N4The g-C is prepared by loading ferric hydroxide on the/TA composite membrane3N4a/TA @ FeOOH-x composite membrane.
Further, the step S1 specifically includes:
s11, adding 0.1-0.3 weight part of tannic acid and 0.04-0.06 weight part of carbon nitride into 50-70 weight parts of deionized water, performing ultrasonic dispersion, centrifuging, and collecting supernatant to obtain g-C3N4And tannic acid TA dispersion;
s12, dissolving 0.05 to 0.15 weight part of trivalent ferric salt in 100 weight parts of water to prepare a trivalent ferric salt solution for later use;
s13, g-C obtained in step S113N4Diluting with tannic acid TA dispersion liquid by adding water, attaching the diluted tannic acid TA dispersion liquid to the surface of a PVDF membrane through reduced pressure filtration, and spraying the ferric salt solution obtained in the step S12 to the surface of the PVDF membrane in the process of reduced pressure filtration.
Further, the ferric salt is FeCl3·6H2O。
Furthermore, the time of ultrasonic dispersion is 1.5h-2.5h, the rotating speed of centrifugation is 7000rpm-8000rpm, and the time of centrifugation is 5min-15 min.
Further, the step S2 specifically includes:
s21, g-C obtained in step S13N4the/TA composite membrane is immersed in FeCl3In solution;
s22, soaking the mixture of the step S21 with g-C3N4FeCl of/TA composite membrane3Putting the solution into a drying oven for hot drying to load ferric hydroxide;
s23, loading iron oxyhydroxide in the step S22Taking out the composite membrane, and drying in a vacuum oven to obtain g-C3N4a/TA @ FeOOH-x composite membrane.
Further, in step S21, FeCl3The concentration of the solution is 0.2 wt% to 0.6 wt%.
Further, in step S22, the temperature of the oven is 50-70 ℃, and the baking time is 5-7 h.
Further, in step S23, the temperature of the vacuum oven is 30-50 ℃, and the drying time is 22-26 h.
The preparation method takes a polyvinylidene fluoride (PVDF) film as a substrate, modifies carbon nitride by utilizing the complexation of ferric ions and tannic acid, and prepares g-C taking the carbon nitride as the substrate3N4the/TA composite membrane is formed by mineralizing the ferric ion in the ferric trichloride solution at g-C3N4The surface of the/TA composite membrane is loaded with iron oxyhydroxide (FeOOH) in situ to construct a micro-nano coarse structure, so that the composite membrane has surface hydrophilic/underwater super oleophobic wettability. Meanwhile, the multifunctional composite membrane with high-efficiency oil-water separation performance and self-cleaning capability under visible light is obtained by utilizing the photo-Fenton catalytic reaction of the hydroxyl ferric oxide.
The invention provides a visible light driven self-cleaning carbon nitride multifunctional composite film prepared by the preparation method.
The third aspect of the invention provides an application of the visible light driven self-cleaning carbon nitride multifunctional composite film, and the visible light driven self-cleaning carbon nitride multifunctional composite film is particularly applied to an oil-water separation technology.
The visible light driven self-cleaning carbon nitride multifunctional composite film prepared by the invention has the beneficial effects that:
(1) the water-based paint has good hydrophilic performance and underwater super-oleophobic wettability, and has higher pure water flux;
(2) the surfactant-stabilized oil-water emulsion has a good separation effect, the separation effect on the emulsion is over 99.0 percent, and the surfactant-stabilized oil-water emulsion has excellent anti-pollution performance;
(3) has good visible light catalytic degradation performance.
Drawings
FIG. 1 is a total reflection infrared (ATR-FTIR) spectrum of a composite membrane;
FIG. 2 shows g-C3N4TA and g-C3N4XRD spectrogram of the/TA @ FeOOH-x composite membrane;
FIG. 3 is a surface wetting performance test chart of a membrane;
FIG. 4 is an SEM image of a membrane;
FIG. 5 is g-C3N4TA and g-C3N4A pure water flux test chart of the/TA @ FeOOH-x composite membrane;
FIG. 6 is a graph showing the oil-water separation performance and separation effect of the membrane;
FIG. 7 is g-C3N4A cycle test plot of/TA @ FeOOH-1;
FIG. 8 is g-C3N4The degradation effect diagram of the/TA @ FeOOH-1 composite membrane on methylene blue under visible light.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment provides a preparation method of a visible light driven self-cleaning carbon nitride multifunctional composite film, which comprises the following steps:
(1)g-C3N4preparation of/TA composite membrane
The complexation of tannic acid molecules and ferric ions is utilized to realize the g-C pair3N4The surface modification of the PVDF membrane is realized by a method of vacuum filtration, and g-C is prepared3N4A/TA composite membrane. The specific experimental steps are as follows: mixing 0.1-0.3 g Tannic Acid (TA) and 0.04-0.06 g carbon nitride C3N4Dispersing in 50mL-70mL deionized water, ultrasonic dispersing for 1.5-2.5 h, centrifuging the dispersion at 7000-8000rpm for 5-15min, collecting the upper layer liquid, and preparing g-C3N4And tannic acid TA dispersion. Preparation of FeCl3Solution (0.05-0.15 g FeCl3·6H2O dissolved in 100mL water). Taking the above TA-g-C3N41.0-2.0mL of dispersion, diluting with water to 50mL, pumping membrane with water pump (PVDF membrane is hydrophilic 0.22 μm), and adding 5-15mL of FeCl during pumping filtration3Spraying the solution on the surface of the membrane, and carrying out vacuum filtration to obtain g-C3N4a/TA membrane.
(2)g-C3N4Iron oxyhydroxide loaded on/TA composite membrane
Mixing the above g-C3N4A TA membrane immersed in FeCl at a concentration of 0.2-0.6 wt%3Putting the solution into an oven at 50-70 ℃ in the aqueous solution, and standing for 5-7 hours. After the reaction, taking out the composite membrane loaded with the FeOOH, and drying the composite membrane in a vacuum oven (the drying temperature is 30-50 ℃) for 22-26h to obtain g-C3N4/TA@FeOOH-x。
Example 1
Mixing 0.2g of Tannic Acid (TA) with 0.05g of carbon nitride C3N4Dispersing in 60mL deionized water, ultrasonically dispersing for 2 hours, centrifuging the dispersion liquid at 8000rpm for 10min, collecting the upper layer liquid, and preparing g-C3N4And tannic acid TA dispersion. Preparation of FeCl3·6H2O solution (0.1 g FeCl3·6H2O dissolved in 100mL water). Taking the above TA-g-C3N41.5mL of dispersion, diluting to 50mL with water, pumping membrane with water (PVDF membrane is hydrophilic 0.22 μm), and loading 10mL FeCl during pumping filtration3·6H2Spraying the O solution on the surface of the membrane, and carrying out vacuum filtration to obtain g-C3N4a/TA membrane.
Mixing the above g-C3N4the/TA film is immersed in FeCl of ferric chloride with the concentration of 0.2 wt%3·6H2O aqueous solution, the solution was placed in an oven at 60 ℃ and left to stand for 6 hours. After the reaction, taking out the composite membrane loaded with the FeOOH, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the g-C3N4a/TA @ FeOOH-1 composite membrane.
Example 2
The other characteristics are the same as those of embodiment 1, except forIs characterized by g-C3N4the/TA film is immersed in FeCl of ferric chloride with the concentration of 0.4 wt%3·6H2In an aqueous solution of O to obtain g-C3N4a/TA @ FeOOH-2 composite membrane.
Example 3
The remaining characteristics are the same as in example 1, except that g-C3N4the/TA film is immersed in FeCl of ferric chloride with the concentration of 0.6 wt%3·6H2In an aqueous solution of O to obtain g-C3N4a/TA @ FeOOH-3 composite membrane.
Comparative example
The remaining characteristics are the same as in example 1, except that g-C3N4the/TA film is not immersed in FeCl3·6H2In an aqueous solution of O.
Examples of the experiments
Adopting FTIR, XPS, XRD, SEM and other instruments to process the g-C3N4A/TA @ FeOOH-1 composite membrane g-C3N4A/TA @ FeOOH-2 composite membrane g-C3N4the/TA @ FeOOH-3 composite membrane (for convenience of description, g-C can be unified3N4the/TA @ FeOOH-x composite membrane is named) and g-C3N4The chemical composition, the micro-morphology and the structure of the/TA membrane are characterized. The wetting property, water flux, anti-contamination property, separation efficiency of oil-water emulsion, and self-cleaning ability of the composite membrane surface were evaluated.
(1) FIG. 1 is a total reflection infrared (ATR-FTIR) spectrum of a composite membrane. In g-C3N41719cm in infrared spectrum of/TA composite membrane-1And 1406cm-1Respectively represents the stretching vibration peaks of-C ═ O and-C-O in the tannin molecule, and shows that the Tannin (TA) is successfully deposited on g-C through the complexation with iron ions3N4And obtaining g-C by vacuum filtration3N4A/TA composite membrane. g-C3N4In an infrared spectrogram of the/TA @ FeOOH-x composite membrane, the infrared spectrums are all 838cm-1And 668cm-1A characteristic absorption peak appears, the characteristic peak is a stretching vibration peak of Fe-O and Fe-O-Fe formed after the ferric trichloride is hydrolyzed, and in addition, the absorption peak is in the range of 3000-3600cm-1Hydroxy radicalThe absorption peak of the radical is g-C3N4the/TA composite membrane is obviously enhanced, which shows that g-C3N4the/TA composite membrane is hydrolyzed in ferric trichloride solutions with different concentrations and successfully loads ferric oxyhydroxide.
(2) FIG. 2 shows g-C3N4TA and g-C3N4XRD spectrogram of the/TA @ FeOOH-x composite membrane; comparison of g to C3N4XRD pattern of/TA film at g-C3N4In XRD spectrogram of the/TA @ FeOOH-x composite membrane, characteristic diffraction peaks appear at 12 degrees (110), 26.9 degrees (310), 35.4 degrees (211), 39.4 degrees (301) and 56.2 degrees (521), which indicates the existence of the iron oxyhydroxide, and indicates that the characteristic diffraction peaks appear at g-C3N4The surface of the/TA @ FeOOH-x composite membrane successfully loads iron oxyhydroxide through mineralization.
(3) The surface wettability of the membrane is an important performance index of the oil-water separation membrane, and g-C is represented by adopting a contact angle test3N4TA and g-C3N4The wetting property of the/TA @ FeOOH-x composite membrane is shown in FIG. 3(a), and the results of the wetting of the surface of each composite membrane by water in the air are shown. As can be seen from FIG. 3(a), when the water drops come into contact with g-C3N4/TA、g-C3N4/TA@FeOOH-1、g-C3N4/TA@FeOOH-2、g-C3N4The Water Contact Angles (WCA) of the/TA @ FeOOH-3 composite membrane on the surface are respectively 55.5 degrees, 45.0 degrees, 43.6 degrees and 29.2 degrees. Description of g-C3N4TA and g-C3N4the/TA @ FeOOH-x composite membrane has good hydrophilic performance in air. From the change of the contact angle with time (fig. 3(a)), the Water Contact Angle (WCA) of each composite film rapidly decreased to 0 ° in a short time. And after the hydroxyl ferric oxide is loaded, the hydrophilicity of the composite membrane is obviously improved, because the hydroxyl ferric oxide loaded on the surface has strong hydrophilic performance, and meanwhile, the hydroxyl ferric oxide generated by in-situ mineralization on the surface of the membrane has a micro-nano rough structure, thereby being beneficial to the adsorption of the hydroxyl ferric oxide with high surface energy to water molecules and showing stronger hydrophilic capability.
The result of the measurement of the underwater oil contact angle shows that g-C3N4/TA、g-C3N4/TA@FeOOH-1、g-C3N4/TA@FeOOH-2、g-C3N4The underwater Oil Contact Angles (OCA) of the/TA @ FeOOH-3 composite membrane were 145.7 °, 156.7 °, 157.5 °, and 159.2 °, respectively (see FIG. 3 (c)). After the FeOOH is loaded, the underwater oil contact angles of the composite membrane are all larger than 150 degrees, the underwater super-oleophobic property is reflected, and the g-C prepared by the method is illustrated3N4the/TA @ FeOOH-x composite membrane has a rough structure with high surface energy, and is beneficial to capturing water molecules by the composite membrane to form a water membrane, so that the contact area between oil drops and the surface of the membrane is reduced. The composite membrane shows the underwater super oleophobic performance. Furthermore, g-C3N4The underwater oil contact angle test of the/TA @ FeOOH-1 composite membrane (see figure 3(d)) shows that the composite membrane has good oil stain adhesion resistance.
(4) The pore structure of the membrane surface determines the selectivity and permeability of the membrane, and the separation performance of the membrane can be further analyzed from the microstructure of the surface and section of the composite membrane intuitively by using a Scanning Electron Microscope (SEM). FIGS. 4(a-C) are pure PVDF membrane (0.22 μm), g-C, respectively3N4A/TA composite film and g-C3N4SEM picture of/TA @ FeOOH-2 composite membrane. Wherein FIG. 4(a) a micro-topography of a pure PVDF membrane, with uniform and large pores on the membrane surface, through a carbon nitride/tannin complex (g-C)3N4Per TA) surface modification of pure PVDF membrane, the porosity of the membrane surface is obviously reduced, and g-C on the membrane surface can be observed3N4The lamellar structure of (a) (see fig. 4(b)) shows that carbon nitride is successfully deposited on the surface of the PVDF film under the action of tannic acid and ferric chloride. FIG. 4(C, C1) is g-C3N4SEM images of the/TA @ FeOOH-2 composite membrane from which a large number of grain structures were observed and the roughness of the surface increased, indicating the presence of iron oxyhydroxide (FeOOH) mineralizers. In further contrast to FIG. 4(b), g-C can be observed3N4The lamellar structure of the/TA @ FeOOH-2 composite membrane has large and small particles, which shows that g-C3N4the/TA composite membrane is successfully hydrolyzed in the ferric trichloride solution to form the hydroxyl ferric oxide.
(5) The magnitude of the membrane flux is closely related to the membrane structure and the hydrophilicity of the membrane. Microporous membrane with high average pore diameter, large porosity and loose membrane structure, and its preparation methodThe water has lower transmembrane resistance and thus higher pure water flux. The membrane with higher hydrophilicity has better affinity with water and helps water molecules to pass through the membrane, so the membrane with higher hydrophilicity also has higher water flux. For the prepared g-C3N4A/TA composite membrane and a series of g-C3N4The pure water flux of the/TA @ FeOOH-x composite membrane was measured, and the results are shown in FIG. 5. The results show that g-C3N4/TA、g-C3N4/TA@FeOOH-1、g-C3N4/TA@FeOOH-2、g-C3N4The pure water flux of/TA @ FeOOH-3 is 4777.07 L.m-2·h-1·bar-1、3724.3L·m-2·h-1·bar-1、3444.47L·m-2·h-1·bar-1、3196.1L·m-2·h-1·bar-1. The results show that the three composite membranes have higher pure water flux, and the water flux of the composite membrane has a small-amplitude reduction trend after the ferric hydroxide is loaded, because the compact ferric hydroxide oxide (FeOOH) is in the g-C range3N4The pore diameter of the composite membrane is reduced by the load of the/TA, so that the membrane passing resistance of water molecules is increased, and the water flux of the membrane is reduced. And the degree of decrease of the water flux increases with the increase of the concentration of the ferric trichloride solution, which shows that g-C3N4The amount of the iron oxyhydroxide (FeOOH) formed by the/TA composite membrane in a high-concentration ferric trichloride solution is larger, so that the surface pores of the membrane are denser, and the reduction amplitude of the water flux is increased.
(6) FIG. 6 shows g-C3N4TA and g-C3N4A separation performance diagram of the/TA @ FeOOH-x composite membrane on an oil-water emulsion. FIG. 6(a) shows the effect of separating the composite membranes from the n-hexane emulsion (containing SDS). Indicates g-C3N4/TA、g-C3N4/TA@FeOOH-1、g-C3N4/TA@FeOOH-2、g-C3N4the/TA @ FeOOH-3 composite membrane has good separation effect on normal hexane emulsion, and the separation efficiency on the emulsion reaches more than 99.0%; description of g-C3N4TA and g-C3N4the/TA @ FeOOH-x composite membranes can quickly stabilize oil-water emulsionDemulsification is carried out, and oil-water separation is effectively realized. Experiments show that g-C is obtained after loading the iron oxyhydroxide3N4The separation performance of the/TA @ FeOOH-x composite membrane is improved, because the strong hydrophilicity of the hydroxyl ferric oxide enhances the separation performance of the composite membrane to emulsion. With the increase of the concentration of the ferric trichloride solution, the flux has the tendency of gradually reducing, because the loading capacity of FeOOH (FeOOH) on the surface of the composite membrane is increased with the increase of the concentration of the ferric trichloride solution, a more compact pore structure is formed on the surface, and the separation flux of the composite membrane is reduced. The results show that g-C3N4the/TA @ FeOOH-1 composite membrane shows excellent performance in the aspects of oil-water separation efficiency and separation flux.
Meanwhile, FIG. 6(b, C) is g-C3N4The separation performance of the/TA @ FeOOH-1 composite membrane on different oil-water emulsions is improved. The results show that g-C3N4the/TA @ FeOOH-1 composite membrane has higher separation performance on normal hexane, petroleum ether, toluene, cyclohexane and diesel emulsion respectively. However, the treatment throughput varies from oil to water emulsion, depending on the adhesion properties of the different oils and their concentration in the emulsion.
(7) The g-C is investigated here by means of a cycling test3N4The anti-pollution performance of the/TA @ FeOOH-1 composite membrane. The SDS-stabilized diesel oil-water emulsion was used as a contamination model in the test, as can be seen from FIG. 7, g-C was measured during the nine-cycle test3N4the/TA @ FeOOH-1 composite membranes show good separation performance for diesel oil-water emulsion. At the same time, g-C is present during the cycle3N4The water flux of the/TA @ FeOOH-1 composite membrane and the flux of the processed emulsion are not greatly attenuated, and the water flux is still kept at 3588 L.m-2·h-1·bar-1This is because the g-C is not only increased after loading iron oxyhydroxide3N4the/TA @ FeOOH-1 composite membrane has hydrophilic capacity on the surface, and meanwhile, the iron oxyhydroxide grown in situ constructs a micro-nano rough structure on the membrane surface, so that water molecules can quickly form a hydration membrane on the membrane surface, and the adhesion of oil stains to the membrane surface is reduced, therefore, the membrane surface can be cleaned by pure waterThe water flux is now restored. The results of the cycle tests show that g-C3N4the/TA @ FeOOH-1 composite membrane has good anti-pollution capacity and higher reuse rate, and improves the repeated operability and the service life of the composite membrane in application.
(8) FIG. 8 is g-C3N4The result of a degradation experiment of the/TA @ FeOOH-1 composite membrane on pollutants on the surface of the membrane under visible light. In the test of g-C3N4During the photo-Fenton catalytic reaction activity of the/TA @ FeOOH-1 composite membrane, Methylene Blue (MB) is adopted as a pollutant, a 20ppm methylene blue solution is prepared, and the degradation performance of the composite membrane on organic pollutants under visible light is investigated. The results are shown in FIG. 8, g-C under visible light3N4the/TA @ FeOOH-1 composite membrane realizes the complete degradation of MB dye within 50 min. The concentration of methylene blue in the solution was characterized by its uv-vis absorption peak (see fig. 8(a)), a strong absorption peak was observed at 664nm before treatment, and the absorption peak gradually decreased with increasing light irradiation time, indicating that the concentration of methylene blue in the solution gradually decreased, and that full degradation of Methylene Blue (MB) was achieved after 50min of treatment. The experimental results show that g-C3N4the/TA @ FeOOH-1 composite membrane has excellent visible light Fenton catalytic activity, can effectively degrade organic pollutants on the surface of the membrane in a short time, and shows that g-C3N4the/TA @ FeOOH-1 composite film has good visible light driven self-cleaning capability.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a visible light driven self-cleaning carbon nitride multifunctional composite film is characterized by comprising the following steps:
s1, preparation g-C3N4a/TA composite membrane;
s2, g-C obtained in step S13N4The g-C is prepared by loading ferric hydroxide on the/TA composite membrane3N4a/TA @ FeOOH-x composite membrane.
2. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 1, wherein the step S1 specifically comprises:
s11, adding 0.1-0.3 weight part of tannic acid and 0.04-0.06 weight part of carbon nitride into 50-70 weight parts of deionized water, performing ultrasonic dispersion, centrifuging, and collecting supernatant to obtain g-C3N4And tannic acid TA dispersion;
s12, dissolving 0.05 to 0.15 weight part of trivalent ferric salt in 100 weight parts of water to prepare a trivalent ferric salt solution for later use;
s13, g-C obtained in step S113N4Diluting with tannic acid TA dispersion liquid by adding water, attaching the diluted tannic acid TA dispersion liquid to the surface of a PVDF membrane through reduced pressure filtration, and spraying the ferric salt solution obtained in the step S12 to the surface of the PVDF membrane in the process of reduced pressure filtration.
3. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 2, wherein the ferric salt is FeCl3·6H2O。
4. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 2, wherein the time of ultrasonic dispersion is 1.5h-2.5h, the rotation speed of centrifugation is 7000rpm-8000rpm, and the time of centrifugation is 5min-15 min.
5. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 1, wherein the step S2 specifically comprises:
s21, g-C obtained in step S13N4the/TA composite membrane is immersed in FeCl3In solution;
s22, soaking the mixture of the step S21 with g-C3N4FeCl of/TA composite membrane3Putting the solution into a drying oven for hot drying to load ferric hydroxide;
s23, taking out the composite film loaded with the iron oxyhydroxide in the step S22, and putting the composite film into a vacuum oven for drying to obtain g-C3N4a/TA @ FeOOH-x composite membrane.
6. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 5, wherein in step S21, FeCl3The concentration of the solution is 0.2 wt% to 0.6 wt%.
7. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 5, wherein in step S22, the temperature of the oven is 50-70 ℃, and the baking time is 5-7 h.
8. The method for preparing the visible light driven self-cleaning carbon nitride multifunctional composite film according to claim 5, wherein in step S23, the temperature of the vacuum oven is 30-50 ℃, and the drying time is 22-26 h.
9. A visible light driven self-cleaning carbon nitride multifunctional composite film, which is prepared by the preparation method of claims 1-8.
10. The use of the multifunctional visible light driven self-cleaning composite carbon nitride film as claimed in claim 9, wherein the composite film is used in oil-water separation technology.
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